JP6587249B2 - Textile processing adhesive composition and textile product - Google Patents

Description

  The present invention relates to an adhesive composition for fiber processing and a fiber product. Specifically, it is an adhesive composition used when producing a textile product, and the textile product obtained using the adhesive composition has a small dimensional change during washing and has a drainability during washing dehydration. It relates to adhesive compositions and textiles that are good.

In general, textile products such as rugs, such as tufted carpets, use a water-based adhesive composition for fiber processing to prevent the pile yarn from slipping out and stabilize the size of the carpet, and fix the pile yarn to the primary base fabric. ing. Moreover, applying a water-based adhesive composition for fiber processing to the back surface of a rug has been performed as a prevention of displacement when the rug is laid in a room or the like. Furthermore, there are cases where a secondary base fabric is adhered to the back surface of the primary base fabric in order to give cushioning properties to the rug or to improve the appearance quality, and an aqueous adhesive composition for fiber processing is used. . Thus, a water-based adhesive composition for fiber processing has been conventionally used.

  By the way, textile products gradually become dirty while they are being used, and sometimes spills and gets dirty, and there is a need to wash them at home and use them for a long time. For this reason, when the textile is soiled, it must be washable in a washing machine and have a wash resistance that can be reused after the washing process.

However, textile products that use water-based adhesive compositions, when washed with water, the adhesive layer swells with moisture. However, the appearance may be impaired, and when there is a large amount of swelled moisture, drying is slow.

As a means for increasing the washing resistance, for example, Patent Document 1 discloses that the backing layer contains a release agent, or the release layer is applied to the surface of the backing material, thereby causing friction of the backing layer during the washing process. It is disclosed that it is possible to suppress damage to the backing layer by reducing the thickness of the backing layer.
Further, for example, in Patent Document 2, a quaternary ammonium cationic antibacterial agent (A), a fluorine-containing water- and oil-repellent agent (B), and a urethane resin flame retardant agent (C) are added to the synthetic fiber surface of the pile portion. It has been proposed to improve the washing resistance by applying.

  However, satisfactory solutions have not yet been obtained to solve the above-mentioned problems.

JP-A-57-172066

Japanese Patent Laid-Open No. 5-33270

The object of the present invention is excellent in washing resistance, which is difficult to solve with the prior art, can solve problems such as swelling with water and changing dimensions when washing with water, and slow drying. It is an object of the present invention to provide an adhesive composition for fiber processing and a fiber product.

The present invention is an adhesive composition for fiber processing, wherein the adhesive composition is an aqueous adhesive composition containing a carboxy-modified resin emulsion and a water repellent. It uses things.

When the textile composition is processed using the adhesive composition, the adhesive composition of the present invention has a small dimensional change at the time of washing, and has good drainage properties at the time of dehydration, so that it dries quickly. It is possible to obtain a textile product that is less likely to cause appearance defects such as warping and waviness after drying.

The present invention is described in detail below.
The carboxy-modified resin emulsion used in the adhesive composition of the present invention is an aqueous dispersion of a copolymer of an ethylenically unsaturated carboxylic acid monomer and a monomer copolymerizable therewith. A saturated carboxylic acid monomer is contained in an amount of 0.3% by weight to 5% by weight.

  Examples of the ethylenically unsaturated carboxylic acid monomer include mono- or dicarboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, or anhydrides thereof. These monomers can be used individually by 1 type or in combination of 2 or more types. These monomers are 0.3% by weight or more and 5% by weight or less, preferably 0.5% by weight or more and less than 3% by weight, based on the total monomers constituting the copolymer. When the amount of the ethylenically unsaturated carboxylic acid monomer is less than 0.3% by weight, the compounding property of the adhesive composition and the take-off strength of the processed fiber product tend to decrease, and when it exceeds 5% by weight, the carboxy-modified resin emulsion There is a tendency that the viscosity of the resin is high and troubles are likely to occur in handling, and the water resistance tends to decrease.

  Monomers that can be copolymerized with the ethylenically unsaturated carboxylic acid monomer include conjugated diene monomers, aromatic vinyl monomers, ethylenically unsaturated carboxylic acid alkyl ester monomers, and hydroxyl groups. Ethylenically unsaturated monomers containing vinyl, vinyl cyanide monomers, ethylene, propylene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, and the like. It can be used above. These monomers are 95 weight% or more and 99.7 weight% or less with respect to all the monomers which comprise a copolymer, Preferably they are 97 weight% or more and 99.5 weight% or less. Among these, a carboxy-modified diene copolymer containing an ethylenically unsaturated carboxylic acid monomer and a conjugated diene monomer is preferable from the viewpoint of excellent balance between texture and strength of the obtained fiber product.

  When the resin emulsion is a carboxy-modified diene copolymer, a monomer composed of an ethylenically unsaturated carboxylic acid monomer, a conjugated diene monomer, and other monomers copolymerizable therewith. It is obtained by copolymerizing the monomer.

Conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted straight chain And monomers such as conjugated pentadienes, substituted and side chain conjugated hexadienes. These can be used individually by 1 type or in combination of 2 or more types. In particular, the use of 1,3-butadiene is preferred.
The conjugated diene monomer is preferably 20% by weight or more and 60% by weight or less with respect to all monomers constituting the copolymer. More preferably, they are 30 weight% or more and 50 weight% or less. When the amount of the conjugated diene monomer is less than 20% by weight, the texture of the resulting fiber product tends to be hard, and when it is more than 60% by weight, the yarn removal strength and peel strength of the resulting fiber product tend to decrease. .

As the monomer copolymerizable with the ethylenically unsaturated carboxylic acid monomer and the conjugated diene monomer, each monomer (conjugated diene) copolymerizable with the above-mentioned ethylenically unsaturated carboxylic acid monomer is used. Can be used).
The monomer copolymerizable with the ethylenically unsaturated carboxylic acid monomer and the conjugated diene monomer is 35% by weight or more and 79.7% by weight or less based on the total monomers constituting the copolymer. Is preferred. More preferably, it is 47 weight% or more and 69.5 weight% or less.

The carboxy-modified resin emulsion used in the adhesive composition of the present invention is obtained by copolymerizing each monomer by a known method. Among these, emulsion polymerization is preferable. The addition method of various components in emulsion polymerization is not particularly limited, and any of a batch addition method, a divided addition method, a continuous addition method, and a power feed method can be adopted. As the polymerization method, batch polymerization, semi-batch polymerization, seed polymerization and the like can be used.
Furthermore, in the case of emulsion polymerization, conventional emulsifiers, chain transfer agents, polymerization initiators, hydrocarbon solvents, electrolytes, chelating agents, polymerization accelerators and the like can be used.

  Emulsifiers used for emulsion polymerization include anions such as higher alcohol sulfates, alkylbenzene sulfonates, alkyl diphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, and aliphatic sulfate salts. Surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkylene alkyl ethers, nonionic surfactants such as polyoxyethylene derivatives, and amphoteric surfactants such as betaine types are used in combination of one or more. There is no limitation on the type and amount as long as the performance of the adhesive composition is not impaired.

  The chain transfer agent used during the polymerization is n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan, or the like, dimethylxanthogen disulfide, diisopropyl Xanthogen compounds such as xanthogen disulfide, terpinolene, thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, α-methylstyrene dimer, 2,6-di-t-butyl-4-methyl Halogenation of phenolic compounds such as phenol and styrenated phenol, allyl compounds such as allyl alcohol, dichloromethane, dibromomethane and carbon tetrabromide Hydrogenated compounds, vinyl ethers such as α-benzyloxystyrene, α-benzyloxyacrylonitrile, α-benzyloxyacrylamide, triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexylthioglyco A rate etc. are mentioned, These can be used 1 type or 2 or more types.

  As a polymerization initiator used at the time of polymerization, water-soluble polymerization initiators such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators, and oil-soluble polymerization initiators such as benzoyl peroxide can be appropriately used. . In particular, the use of a water-soluble polymerization initiator is preferred.

  Also, during polymerization, unsaturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cycloheptane, etc., unsaturated hydrocarbons such as pentene, hexene, heptene, cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene, 1-methylcyclohexene, etc. Hydrocarbon solvents such as aromatic hydrocarbons such as hydrogen, benzene, toluene and xylene may be used.

The carboxy-modified resin emulsion used in the adhesive composition of the present invention preferably has a total content of sodium and potassium of 5500 ppm or less based on the solid content of the resin emulsion. When the total content of sodium and potassium exceeds 5500 ppm, there is a tendency that the dimensional change at the time of washing of the textile product using the adhesive composition of the present invention becomes large and the drainability at the time of dehydration tends to be inferior. More preferably, it is 3500 ppm or less, and most preferably 2500 ppm or less.
Sodium and potassium contained in the resin emulsion are brought in from polymerization aids such as a polymerization initiator, an emulsifier, an electrolyte, and a pH adjuster used when the emulsion is polymerized. The polymerization aids can be used in combination with the above-mentioned known ones without any particular limitation. To make the total content of sodium and potassium in the finally obtained resin emulsion 5500 ppm or less, the above polymerization aids are used. This can be achieved by adjusting the type and amount used. Specifically, for example, when sodium persulfate is used as a polymerization initiator, the amount of emulsifier, electrolyte and pH adjuster is reduced, or a type not containing sodium and potassium is used. It is possible to adjust to the above-mentioned range by combining.

In addition, the total content of sodium and potassium in the resin emulsion is determined based on the alkali metal element by inductively coupled plasma emission spectroscopic analysis (ICP-AES: SPS4000 manufactured by Seiko Denshi Kogyo Co., Ltd.) after thermally decomposing the synthetic emulsion with sulfuric acid and nitric acid The amount of the alkali metal element obtained is calculated as the concentration (ppm) relative to the solid content of the resin emulsion.

As the water repellent used in the adhesive composition of the present invention, a wax-based water repellent is used. Examples of the wax-based water repellent include natural wax, polyethylene wax, and paraffin wax, which can be used alone or in combination of two or more.

  The adhesive composition of the present invention contains a carboxy-modified resin emulsion and a water repellent, but the water repellent is 0.1 part by weight (solid content) with respect to 100 parts by weight (in terms of solid content) of the carboxy-modified resin emulsion. Conversion) to 15 parts by weight (in terms of solid content) or less. When the water repellent is less than 0.1 parts by weight (in terms of solid content), drainage tends to be lowered. Even if it exceeds 15 parts by weight (in terms of solid content), the improvement in performance commensurate with the amount added is small. More preferably, it is 0.3 parts by weight or more and 10 parts by weight or less.

  The adhesive composition of the present invention can further contain a filler. The filler is not particularly limited, but an inorganic filler such as calcium carbonate, clay, aluminum hydroxide, magnesium hydroxide, barium sulfate, zeolite, zinc oxide, and satin white, or an organic filler such as polyolefin powder is 1 Species or two or more can be used. The amount of the filler used is preferably less than 100 parts by weight (in terms of solid content) with respect to 100 parts by weight (in terms of solid content) of the resin emulsion. If it is 100 parts by weight (in terms of solid content) or more, the washing durability and water resistance of the resulting textile product tend to be reduced. More preferably, they are 30 to 80 weight part, More preferably, they are 50 to 70 weight part.

  In the adhesive composition of the present invention, other additives such as low molecular weight polyacrylic acid, alkylnaphthalenesulfonic acid, tripolyphosphoric acid and salts thereof, ultraviolet absorbers, chlorine-based, bromine-based, phosphorus-based Flame retardants such as, antiseptics such as isothiazoline, antibacterial agents, deodorants, pH adjusters such as sodium hydroxide, potassium hydroxide, ammonia, thickeners such as polyacrylate, carboxymethylcellulose, hydroxyethylcellulose, It is also possible to add known additives such as penetrants such as sulfosuccinic acid, antifoaming agents such as silicon and mineral oil, anti-aging agents, color pigments, and fragrances. There are no particular restrictions on the type and amount used, and appropriate amounts can be used as long as the performance as an adhesive composition is not impaired.

  The textile product of the present invention is processed using the adhesive composition of the present invention. Specifically, a fiber product is obtained by fixing or applying the adhesive composition of the present invention to a base fabric.

  The method of fixing or applying the adhesive composition of the present invention to the base fabric is not particularly limited. For example, the adhesive composition is supplied to a coating bath, lifted by a coating roll, applied to the back surface, and applied with a doctor blade or the like. Roll coating method for scraping off excess adhesive composition, direct coating method for directly applying adhesive composition with back side up and scraping excess adhesive composition with doctor roll etc. Can be mentioned. When foaming the adhesive composition, it is preferably 1.2 times or more and 5.0 times or less, more preferably 1.5 times or more and 4.0 times, from the viewpoint of ease of work in the fixing or coating process. It is preferable to foam to 2 times or less.

The form of the fiber product of the present invention is not particularly limited, and examples thereof include tufted, woven fabric, pile woven fabric, knitted fabric, pile knitted fabric, three-dimensional knitted fabric, and non-woven fabric.
Further, the fibers constituting the fiber product of the present invention are not particularly limited, and those made of synthetic fibers such as polyester fibers, polyamide fibers, polypropylene fibers, acrylic fibers, rayon fibers, etc. can be suitably used. Those made of natural fibers such as cotton and wool can also be used.
As a textile product of the present invention, for example, in a tufted carpet, pile yarn is planted on a primary base fabric, and the adhesive composition of the present invention is applied to the back surface of the primary base fabric, followed by drying and curing. Thus, the pile yarn can be fixed to the primary base fabric, the dimension of the tufted carpet can be stabilized, and the dimensional change when washing is small, and the carpet is excellent in drainage at the time of dehydration.
Furthermore, the secondary base fabric may be adhered to the back surface of the primary base fabric in order to improve the back surface quality of the rug or impart cushioning properties. In this case, the adhesive composition of the present invention is applied to the back surface of the primary base fabric. After that, the secondary base fabric can be laminated and integrated by drying and curing after laminating the secondary base fabric.
In addition, as a textile product of the present invention, for example, after applying a design such as a print to the primary base fabric, the adhesive composition of the present invention is applied to the back surface of the primary base fabric, and then dried and cured to achieve dimensional stability. Can be granted. Similar to the case of tufted carpet, the secondary base fabric may be laminated and integrated.
Each fiber product is excellent in dimensional stability during washing and draining during dehydration, so that it can be dried quickly, and there is no possibility that the appearance quality such as warpage and wrinkles will deteriorate after drying. You can get a product.
In addition, although it does not specifically limit as a primary base fabric or a secondary base fabric, A woven fabric, a needle punch nonwoven fabric, a spun bond nonwoven fabric etc. can be mentioned.
In the case of rug use among the textile products of the present invention, the weight of the secondary base fabric is 50 to 1000 g / m ² , the thickness is 0.5 to 15 mm, and the fineness of the constituent fibers is in the range of 0.1 to 30 dtex. It is preferable to set to. When the basis weight of the secondary base fabric is less than 50 g / m ² , the function and quality of the rug are inferior, which is not preferable. If it exceeds 1000 g / m ² , the cost will increase unnecessarily. Most preferably, it is 70-200 g / m < ² >.

After applying the adhesive composition of the present invention to a textile product, it may be heat-treated at a temperature of 100 ° C. to 170 ° C., more preferably 105 ° C. to 130 ° C., for drying and curing. By setting it as this temperature range, it can be compatible that the textile product does not undergo discoloration deterioration and the drying efficiency is increased.
30-500 g / m < ² > (solid content) is preferable, and 50-400 g / m < ² > (solid content) is more preferable, as for the fixed amount or application | coating amount to the textiles of the adhesive composition of this invention. By setting it as the range of this fixed amount or application amount, excellent dimensional stability can be exhibited during washing, and excellent drainage can be exhibited during dehydration.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples, unless the summary is exceeded. In the examples, parts and percentages indicating percentages are based on weight unless otherwise specified. In addition, various physical properties in the examples were evaluated by the following methods. The evaluation results are shown in Table-1 and Table-2.

Evaluation of dimensional change during washing of textile products 1) Prepare a 180cm x 180cm tufted carpet,
Draw a line of four pieces of 150cm x 150cm with a marker. Measure the length in the vertical and horizontal directions before washing.
2) According to JIS L 0217 103 method, after 10 times washing with a washing machine (washing → rinsing → dehydration), the lengths in the vertical and horizontal directions are measured.
3) The dimensional change rate before and after washing is calculated from the following formula (1).
Formula (1): Average value of longitudinal dimensional change rate and lateral dimensional change rate Each vertical dimensional change rate (%) = 100 × (longitudinal length after washing dehydration−vertical length before washing) / Longitudinal length before washing Lateral dimensional change rate (%) = 100 × (lateral length after washing dehydration−lateral length before washing) / lateral length before washing

The absolute value of the dimensional change rate was evaluated in the following four stages.
(Criteria)
“1” ・ ・ There is almost no dimensional change. (Dimension change rate of 0.5% or less in both vertical and horizontal directions)
“2” ··· Some degree of dimensional change. (Dimension change rate in both vertical and horizontal directions is more than 0.5% and less than 0.75%)
"3" · · · Dimensional change is recognized. (Dimensional change rate in both vertical and horizontal directions is more than 0.75% and less than 1.5%)
"4" ··· Significant dimensional change is recognized. (Dimension change rate over 1.5% in both vertical and horizontal directions)

Evaluation of drainability when washing textile products 1) Measure the weight of one tufted carpet.
2) According to JIS L 0217 103 method, measure the weight of the carpet after washing with a washing machine 10 times (washing → rinsing → dehydration).
3) The weight change rate before and after washing is calculated from the following formula (2). In this case, the weight change rate is the residual moisture content.
Formula (2): Rate of change in weight (%) = (weight after washing dehydration−weight before washing) / (weight before washing) × 100
The absolute value of the residual moisture content was evaluated in the following four stages.
(Criteria)
“1” ・ Excellent draining performance. (Residual moisture content 10% or less)
“2”. Good drainage. (Residual moisture content> 10% to 20%)
“3”-Poor drainage. (Residual moisture content> 20% to 30%)
“4”: Drainability is extremely inferior. (Residual moisture content> 30%)

Preparation of carboxy-modified resin emulsions a and b In a pressure-resistant polymerization reactor equipped with a stirrer, pure water in an amount shown in Table 1, an ethylenically unsaturated carboxylic acid monomer, an amount of 10% of other monomers, and Other compounds were charged, stirred well, and heated to 65 ° C. The remaining monomer was continuously added over 9 hours, and the polymerization was terminated when the final polymerization conversion exceeded 96%. Next, after adding the pH adjusting agent shown in Table 1 to these carboxy-modified resin emulsions, unreacted monomers and other low-boiling compounds were removed by distillation under reduced pressure to obtain carboxy-modified resin emulsions a and b. It was.

Preparation of carboxy-modified resin emulsion c In a pressure-resistant polymerization reactor equipped with a stirrer, 160 parts of pure water, 5 parts of butadiene, 4 parts of styrene, 4 parts of acrylonitrile, 2 parts of fumaric acid, 8 parts of cyclohexene, t-dodecyl mercaptan. 05 parts, 1.3 parts of sodium dodecylbenzenesulfonate and 1.2 parts of potassium persulfate were charged, sufficiently stirred, and heated to 65 ° C. 24.5 parts of butadiene, 15 parts of acrylonitrile and 9 parts of acrylic acid are continuously added over 205 minutes, followed by 12.5 parts of butadiene, 21.5 parts of styrene and 0.15 part of t-dodecyl mercaptan over 180 minutes. Then, 2.5 parts of styrene was continuously added over 20 minutes. The polymerization was terminated when the final polymerization conversion rate exceeded 97%. After adding the pH adjuster shown in Table 1 to the obtained carboxy-modified resin emulsion, unreacted monomers and other low-boiling compounds were removed by distillation under reduced pressure to obtain carboxy-modified resin emulsion c. .

Preparation of adhesive composition In accordance with the formulation shown in Table-2, carboxy-modified resin emulsion, water repellent, filler, dispersant, antifoaming agent, anti-aging agent are mixed, and thickener and water are used in appropriate amounts. The adhesive compositions of Examples 1 to 5 and Comparative Examples 1 to 4 of the present invention were prepared by adjusting the solid content to 50 ± 1% and the viscosity of 15000 ± 1000 mPa · s. The viscosity of the adhesive composition was measured at a rotational speed of 12 rpm using a Brookfield viscometer.

Textiles (tufted carpet) Creating <br/> First, polypropylene tape yarn fabric (18 × 13) in the base fabric (basis weight 86 g / ^{m 2),} implantation pile yarn tufting machine, pile length 6.5mm A skin layer having a basis weight of 500 g / m ² was prepared, and then the foaming agent was added to each of the adhesive compositions of Examples 1 to 5 and Comparative Examples 1 to 4, and mechanical foaming (foaming ratio). After 2.5), 400 g / m ^{2 is} applied to the back surface of the skin layer by roll coating, and as a secondary base fabric, a spunbond nonwoven fabric made of polyester fibers (6 dtex, thickness 1.0 mm, basis weight 70 g / m ^2). ) And dried and cured at 130 ° C. for 15 minutes to obtain carpets of Examples 1 to 5 and Comparative Examples 1 to 4, respectively.

  As shown in Table 2, the adhesive compositions shown in Examples 1 to 5, which are the present invention, all had a small dimensional change during washing and were excellent in drainage during dehydration.

  From Table 2, Comparative Example 1 is an adhesive composition for fiber processing that does not contain a water repellent, and has a large dimensional change during washing of textiles using the adhesive composition, and draining during dehydration. It was inferior. In Comparative Example 2, the amount of the ethylenically unsaturated carboxylic acid monomer in the carboxy-modified resin emulsion exceeds the upper limit, the resulting fiber product has a large dimensional change during washing, and is inferior in drainage during dehydration. It was. In Comparative Example 3, when a fluororesin-based water repellent was used as the water repellent, the adhesive composition greatly thickened and could not be applied, and a fiber product could not be obtained. In Comparative Example 4, when a silicone-based water repellent was used as the water repellent, the adhesive composition was not foamed and the coating amount could not be controlled, and the resulting textile product had a large dimensional change during washing. In addition, it was inferior in drainability during dehydration.

As described above, the textile product using the adhesive composition of the present invention has a small dimensional change at the time of washing and good drainage at the time of dehydration. There are few occurrences of defects that impair the appearance of the product, such as wrinkles and waves after washing and drying. Therefore, the fiber product using the adhesive composition of the present invention is very suitable as a washable fiber product.

Claims (4)

Acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, or their anhydrides alone or in combination of two or more with respect to all monomers constituting the copolymer 1 to 1.4% by weight of ethylenically unsaturated carboxylic acid monomer used Te, a conjugated diene monomer from 20 to 60% by weight, and 35 to 79 wt% copolymerizable with these monomers A tufted carpet processed using an adhesive composition for fiber processing containing a carboxy-modified resin emulsion and a wax-based water repellent ,
The pile yarn is either polyester, polypropylene, or a blend of polyester and polypropylene, the residual moisture content during washing dehydration is 20% or less of tufted carpet, and the dimensional change during dehydration is 1.5%. The following is a tufted carpet. The fiber processing adhesive composition is more than 0 parts by weight (solid content conversion) and 100 parts by weight (solid content conversion) with respect to 100 parts by weight of the carboxy-modified resin emulsion (solid content conversion). below, characterized in that it contains, tufted carpet of claim 1. The Textile processing adhesive composition, characterized in that foamed by fixing or applying a 1.2 to 5.0-fold, tufted carpet of claim 1 or 2. A tufted carpet secondary backing was used non-woven fabric, wherein the coating amount of Textile processing adhesive composition is 50 to 400 g / m 2 ^(after drying), claim 1 The tufted carpet according to any one of 3 above.